Name: _________________________________ Section: _____________________

Experiment 11 – Identification of Hydrocarbons

Discussion

The number of known organic compounds totals into the millions. Of these compounds, the
simplest types are those that contain only hydrogen and carbon atoms. These are known as
hydrocarbons. Because of the number and variety of hydrocarbons that can exist, some means
of classification is necessary.

One means of classification depends on the way in which carbon atoms are connected. Chain
aliphatic hydrocarbons are compounds consisting of carbons linked either in a single chain or
in a branched chain. Cyclic hydrocarbons are aliphatic compounds that have carbon atoms
linked in a closed polygon (also referred to as a ring). For example, hexane (single) and 2-
methylpentane (branched) are chain aliphatic molecules, while cyclohexane is a cyclic
aliphatic compound.

hexane 2-methylpentane cyclohexane

Another means of classification depends on the type of bonding that exists between carbons.
Hydrocarbons that contain only carbon-to-carbon single bonds are called alkanes. These are
also referred to as saturated molecules. Hydrocarbons containing at least one carbon-to-carbon
double bond are called alkenes, and compounds with at least one carbon-to-carbon triple bond
are called alkynes. Alkenes and alkynes are referred to as unsaturated molecules. Finally, a
class of cyclic hydrocarbons that contain a closed loop (sextet) of electrons is called aromatic.
With so many compounds possible, identification of the bond type is an important step in
establishing the molecular structure. Quick, simple tests on small samples can establish the
physical and chemical properties of the compounds by class.

Some of the observed physical properties of hydrocarbons result from the nonpolar character
of the compounds. In general, hydrocarbons do not mix with polar solvents such as water or
ethanol (ethyl alcohol). On the other hand, hydrocarbons mix with relatively nonpolar solvents
such as ligroin (a mixture of alkanes), carbon tetrachloride (CCl4), or dichloromethane
(CH2Cl2). Because the density of most hydrocarbons is less than that of water, they will float.
Crude oil and crude oil products (home heating oil and gasoline) are mixtures of hydrocarbons;
when spilled on water, these substances spread quickly along the surface because they are
insoluble in water.

The chemical reactivity of hydrocarbons is determined by the type of bond in the compound.
Unsaturated hydrocarbons (i.e., alkenes and alkynes) react by addition of reagents to the
double or triple bonds. The addition products become saturated, with fragments of the reagent
becoming attached the carbons of the multiple bond. Aromatic compounds, with a higher
carbon-to-hydrogen ratio than nonaromatic compounds, undergo substitution in the presence
of catalysts rather than an addition reaction.

Chemistry M11 Laboratory Manual Page 67

Name: _________________________________ Section: _____________________

1. Reaction with bromine. Unsaturated hydrocarbons react rapidly with bromine in a

solution of carbon tetrachloride or cyclohexane. The reaction is the addition of the
elements of bromine to the carbons of the multiple bonds.

Br

+ Br2
Br
Red Colorless

Br Br

+ 2Br2
Br Br
Red Colorless

The bromine solution is red; the product that has the bromine atoms attached to carbon
is colorless. Thus, a reaction has taken place when there is a loss of color from the
bromine solution and a colorless solution remains. Because alkanes have only single
C–C bonds present, no reaction with bromine is observed; the red color of the reagent
would persist when added. Aromatic compounds resist addition reactions because of
their “aromaticity”: the possession of a closed loop (sextet) of electrons which imparts
extreme stability. These compounds can react with bromine but require the presence of
a catalyst such as iron fillings or aluminum chloride.

2. Reaction with concentrated sulfuric acid. Alkenes react with cold concentrated sulfuric
acid by addition. Alkyl sulfonic acids form as products and are soluble in H2SO4;
subsequent water work-up results in an “–OH” on the more substituted carbon (as
demonstrated in lecture).

OH
H2O
+ H2SO4

Saturated hydrocarbons are unreactive (additions are not possible); alkynes react
slowly and require a catalyst (H2SO4); due to their inherent stability, aromatic
compounds are also unreactive.

3. Reaction with potassium permanganate. Dilute or alkaline solutions of KMnO4 oxidize

unsaturated compounds. Alkanes and aromatic compounds are generally unreactive.
Evidence that a reaction has occurred is observed by the loss of the purple color of
KMnO4 and the formation of the brown precipitate manganese dioxide, MnO2.

OH
3 + 2KMnO4 + 4H2O 3 + 2MnO2 + 2KOH
Purple OH Brown

Chemistry M11 Laboratory Manual Page 68

Name: _________________________________ Section: _____________________

Note that the product formed (which contains two “–OH” groups) is called a
glycol.

Chemistry M11 Laboratory Manual Page 69

Name: _________________________________ Section: _____________________

Procedure

Assume the organic compounds are highly flammable. Use only small quantities. Keep away
from open flames. Assume the organic compounds are toxic and can be absorbed through the
skin. Avoid contact; wash if any chemical spills on your person. Handle concentrated sulfuric
carefully. Flush with water if any spills on your person. Potassium permanganate and bromine
are toxic; bromine solutions are also corrosive. Although the solutions are diluted, they may
cause burns to the skin. Wear gloves when working with these chemicals. Also consider the
following:

1. The hydrocarbons hexane, cyclohexene, and toluene (alkane, alkene and aromatic,
respectively) are available in dropper bottles.

2. The reagents 1% Br2 in cyclohexane, 1% aqueous KMnO4, and concentrated H2SO4

are available in dropper bottles.

3. Unknowns are in dropper bottles labeled A, B, and C. They may include an alkane, an
alkene, and/or an aromatic compound.

4. Test tubes will be suitable for all the tests; mix thoroughly.

5. Dispose of all organic wastes as directed by the instructor. Do not pour them into the
sink!

Physical Properties of Hydrocarbons

1. Water solubility of hydrocarbons. Label six test tubes with the name of the substance
to be tested. Place into each test tube 5 drops of the appropriate hydrocarbon: hexane,
cyclohexene, toluene, unknown A, unknown B, and unknown C. Add about 5 drops of
water dropwise into each test tube. Water is a polar solvent. Is there any separation of
components? Which component is on the bottom; which component is on the top? Mix
the contents. What happens when the contents are allowed to settle? What do you
conclude about the density of the hydrocarbon? Is the hydrocarbon more dense than
water or less dense than water? Record your observations. Save these solutions for
comparison with the next part.

2. Solubility of hydrocarbons in ligroin. Label six test tubes with the name of the
substance to be tested. Place into each test tube 5 drops of the appropriate
hydrocarbons: hexane, cyclohexene, toluene, unknown A, unknown B, and unknown
C. Add about 5 drops of ligroin dropwise into each test tube. Ligroin is a nonpolar
solvent. Is there a separation of components? Is there a bottom layer and a top layer?
Mix the contents. Is there any change in the appearance of the contents before and after
mixing? Compare these test tubes with those from the previous part. Record your
observations. Can you make any conclusion about the density of the hydrocarbons from
what you actually see?

Chemistry M11 Laboratory Manual Page 70

Name: _________________________________ Section: _____________________

Chemical Properties of Hydrocarbons

1. Reaction with bromine. Results provided on data sheet.

2. Reaction with KMnO4. Label six clean, dry test tubes with the name of the substance to
be tested. Place into each test tube 5 drops of the appropriate hydrocarbon: hexane,
cyclohexene, toluene, unknown A, unknown B, and unknown C. Carefully add
(dropwise) 1% aqueous KMnO4 solution; after each drop, shake to mix the solutions.
Keep count of the number of the drops needed to have the color of the permanganate
solution persist; do not add more than 10 drops. Record your observations.

3. Reaction with concentrated H2SO4. Label six clean, dry test tubes with the name of the
substance to be tested. Place into each test tube 5 drops of the appropriate hydrocarbon:
hexane, cyclohexene, toluene, unknown A, unknown B, and unknown C. Place all of
the test tubes in an ice bath. Wear gloves and carefully add (with shaking) 3 drops of
cold, concentrated sulfuric acid to each test tube. Note whether the solution has become
homogeneous or whether a color is produced. (The evolution of heat, the formation of
a homogeneous solution, or the appearance of a color is evidence that a reaction has
occurred.) Record your observations.

4. Unknowns: By comparing the observations you made for your unknowns with that of
the known hydrocarbons, you can identify unknowns A, B, and C. Record their
identities on your data sheet.

Chemistry M11 Laboratory Manual Page 71

Name: _________________________________ Section: _____________________

Data and Calculations for Experiment 12

Physical Properties of Hydrocarbons

Solubility: Does the hydrocarbon mix with the solvent, soluble, or not mix with solvent,
insoluble? Use the observations you make for the solubility tests and determine whether the
hydrocarbons are polar or nonpolar substances.

Density: For water, is the density greater than water (sinks) or less than water (floats)? For
ligroin, can you tell anything about the relative densities?

H2 O Ligroin

Hydrocarbon Solubility Density Solubility Density

Hexane

Cyclohexene

Toluene,

Unknown A

Unknown B

Unknown C

Chemistry M11 Laboratory Manual Page 72

Name: _________________________________ Section: _____________________

Chemical Properties of Hydrocarbons

Hydrocarbon Bromine Test* KMnO4 Test H2SO4 Test

Hexane Red

Cyclohexene Colorless

Toluene,
Red

Unknown A Red

Unknown B Colorless

Unknown C Red

*The results of the bromine test have been provided for you.

Unknown A is ______________________.

Unknown B is ______________________.

Unknown C is ______________________.

Chemistry M11 Laboratory Manual Page 73

Name: _________________________________ Section: _____________________

Questions

1. Below are four organic compounds. The reagent shown is added to the compound. Based
on your studies in this lab, determine the products (if any) that you should observe when
the reactants below are mixed together:
A. + Br2

B. + KMnO4

C. H2O
+ H2SO4

D. + KMnO4

2. A student has two compounds in two separate bottles but with no labels on either one. One
is an alkane, octane (C8H18); the other is 1-hexene (C6H12), an alkene. Based on your
observations in this experiment, what should you see in the following tests?

Octane 1-Hexene
A. Water solubility

B. Ligroin solubility

C. Density versus water

D. Bromine test

E. Permanganate test

3. An unknown compound, believed to be a hydrocarbon, showed the following behavior: no

heat or color appeared when sulfuric acid was added; permanganate solution remained
purple; and the red color of bromine solution was lost only after a catalyst was added. From
the compounds below, circle the ONE that fits the observations.

OR OR OR

4. In your own words, write a one-half page, well-written abstract of the entire experiment,
making sure to briefly state the overall purpose or goal as well as any conclusions. (For
additional guidelines on writing this abstract, please refer to the Moorpark College
Chemistry Department Laboratory Report Rubric found in the lab manual and
department website.)

Chemistry M11 Laboratory Manual Page 74